CN116716075A - Solvent-free environment-friendly modified polyurethane adhesive and preparation method thereof - Google Patents
Solvent-free environment-friendly modified polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN116716075A CN116716075A CN202310676966.6A CN202310676966A CN116716075A CN 116716075 A CN116716075 A CN 116716075A CN 202310676966 A CN202310676966 A CN 202310676966A CN 116716075 A CN116716075 A CN 116716075A
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- polyurethane adhesive
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 65
- 239000000853 adhesive Substances 0.000 title claims abstract description 64
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 45
- 239000004814 polyurethane Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000004359 castor oil Substances 0.000 claims abstract description 50
- 235000019438 castor oil Nutrition 0.000 claims abstract description 50
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 50
- 239000000945 filler Substances 0.000 claims abstract description 37
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 12
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 22
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 22
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- CITFYDYEWQIEPX-UHFFFAOYSA-N Flavanol Natural products O1C2=CC(OCC=C(C)C)=CC(O)=C2C(=O)C(O)C1C1=CC=C(O)C=C1 CITFYDYEWQIEPX-UHFFFAOYSA-N 0.000 claims description 14
- 235000011987 flavanols Nutrition 0.000 claims description 14
- OEIJRRGCTVHYTH-UHFFFAOYSA-N Favan-3-ol Chemical compound OC1CC2=CC=CC=C2OC1C1=CC=CC=C1 OEIJRRGCTVHYTH-UHFFFAOYSA-N 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 239000001361 adipic acid Substances 0.000 claims description 11
- 235000011037 adipic acid Nutrition 0.000 claims description 11
- 239000005543 nano-size silicon particle Substances 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- 229920005862 polyol Polymers 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 10
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 10
- MYOMTFLOYSMNOM-UHFFFAOYSA-N 2,3-dimethylbutane-1,1-diol Chemical compound CC(C)C(C)C(O)O MYOMTFLOYSMNOM-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 20
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- SXSWMAUXEHKFGX-UHFFFAOYSA-N 2,3-dimethylbutan-1-ol Chemical compound CC(C)C(C)CO SXSWMAUXEHKFGX-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000012205 single-component adhesive Substances 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002206 flavan-3-ols Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3218—Polyhydroxy compounds containing cyclic groups having at least one oxygen atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a solvent-free environment-friendly modified polyurethane adhesive and a preparation method thereof, belonging to the technical field of polyurethane adhesives. According to the scheme, the modified filler with a plurality of hydroxyl functional groups and the modified castor oil are introduced to synergistically enhance the adhesion performance of the adhesive, so that the adhesion performance and the mechanical performance of the modified polyurethane adhesive are greatly improved. The solvent-free environment-friendly modified polyurethane adhesive comprises the following raw materials: polypropylene glycol, liquefied MDI, diethanolamine, modified castor oil, phosphoric acid and modified filler.
Description
Technical Field
The invention belongs to the technical field of polyurethane adhesives, and relates to a solvent-free environment-friendly modified polyurethane adhesive and a preparation method thereof.
Background
The solvent-free adhesive is one of polyurethane adhesives, and can be a single-component adhesive or a double-component adhesive, namely, the adhesion and connection of media are realized under the condition of no solvent. Is a potential adhesive which is green and environment-friendly and can be used for food packaging and the like. The solvent-free single-component adhesive belongs to one of solvent-free adhesives, and has been widely applied in various fields of industry, agriculture, transportation, medicine, national defense and daily life. However, because no solvent exists, the viscosity of the adhesive is high, the construction performance in certain fields is poor, the adhesive strength, heat resistance, room temperature curing speed and the like of the adhesive layer are required to be improved, and particularly, the application in high-end fields such as automobiles, airplanes and the like needs to be further modified.
The conventional common modification method for polyurethane, such as internal crosslinking modification, can obviously increase the viscosity of the prepolymer after adding chain extender molecules, and needs to be diluted by adding a solvent; chemical blend modification requires final curing at higher temperatures. Therefore, the polyurethane adhesive with low viscosity and good mechanical property cannot be prepared by the traditional modification method.
Disclosure of Invention
The invention aims to provide a solvent-free environment-friendly modified polyurethane adhesive and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
the solvent-free environment-friendly modified polyurethane adhesive comprises the following raw materials in parts by weight:
40-55 parts of polypropylene glycol, 120-150 parts of liquefied MDI (diphenyl methane diisocyanate), 7-10 parts of diethanolamine, 1-2 parts of modified castor oil, 1-2 parts of phosphoric acid and 8-10 parts of modified filler;
the preparation method of the modified filler comprises the following steps:
1) Adding styrene, divinylbenzene, butyl acrylate and hydroxyethyl methacrylate into deionized water, heating and stirring under nitrogen atmosphere to obtain a mixed solution;
2) Pretreating the mixed solution, adding flavanol and potassium persulfate aqueous solution under nitrogen atmosphere, stirring for reaction, cooling to room temperature, and filtering to remove gel to obtain emulsion;
3) And centrifuging, drying and grinding the emulsion to obtain the modified filler.
According to the scheme, the viscosity of the modified polyurethane adhesive is reduced by introducing the modified filler with a plurality of hydroxyl functional groups, the addition of the modified castor oil increases the intersolubility of partial components of the system, and meanwhile, the modified castor oil and the modified filler have the synergistic effect of improving the rheological property of the adhesive, and the modified castor oil contains more double bonds and triple bonds and can be used as a softener and a plasticizer to improve the rheological property of the adhesive, so that the fluidity of the adhesive is improved; in addition, the modified filler and the modified castor oil synergistically enhance the adhesion performance of the adhesive, because the hydroxyl functional groups can react with the modified castor oil to form chemical bonds, thereby enhancing the adhesion performance, mechanical strength and thermal stability of the adhesive, and the modified castor oil can improve the flexibility and heat resistance of the adhesive.
As a preferable technical scheme of the invention, in the step 1), the heating condition is that the temperature is heated to 75-80 ℃, and the stirring and mixing time is 30-45min.
As a preferable technical scheme of the invention, in the step 2), the pretreatment is to cool the mixed solution to 40-45 ℃ and adjust the pH value to 4.5-5.5; the stirring reaction time is 4-5h; the mass concentration of the potassium persulfate aqueous solution is 99.5%.
As a preferable technical scheme of the invention, in the steps 1) -2), the mass ratio of the styrene, divinylbenzene, butyl acrylate, hydroxyethyl methacrylate, deionized water, flavanol and potassium persulfate aqueous solution is 10-11:6.7-7.0:3.2-3.5:8.2-8.8:970-980:1.5-2.5:1.2-5.2.
As a preferable technical scheme of the invention, the particle size of the ground modified filler is 400-500nm.
The invention discloses a preparation method of modified castor oil, which comprises the following steps:
(1) Stirring and mixing 2, 3-dimethylbutanediol, adipic acid, isophthalic acid, polyether polyol and nano silicon dioxide, and heating for reaction to obtain a mixture;
(2) Mixing the mixture with castor oil, and heating to react to obtain the modified castor oil.
As a preferable technical scheme of the invention, in the step (1), the stirring and mixing conditions are that stirring is carried out for 30-45min at the rotating speed of 250-300 r/min; the heating reaction condition is that the reaction is carried out for 10 to 12 hours under the vacuum state at the temperature of 210 to 220 ℃; the mass ratio of the isophthalic acid to the 2, 3-dimethylbutanediol to the adipic acid to the polyether polyol to the nano silicon dioxide is 10-11:75-80:80-88:8-9:0.08-0.1.
As a preferable technical scheme of the invention, in the step (2), the mass ratio of the mixture to castor oil is 2.0-2.2:1, the heating reaction condition is that the reaction is carried out for 3 to 4 hours under the vacuum state at the temperature of 210 to 220 ℃.
The scheme of the invention discloses a preparation method of a solvent-free environment-friendly modified polyurethane adhesive, which comprises the following steps: and (3) uniformly mixing the modified filler with polypropylene glycol, heating in a nitrogen atmosphere, and sequentially adding liquefied MDI, diethanolamine, modified castor oil and phosphoric acid for reaction to obtain the modified polyurethane adhesive.
As a preferable technical scheme of the invention, the uniform mixing condition is ultrasonic dispersion for 30-45min, the heating condition is heating to 70-75 ℃ and the reaction time is 3-5h.
As a preferred embodiment of the present invention, the liquefied MDI is analytically pure liquefied MDI1635, available from Bayer (China).
The invention has the beneficial effects that:
(1) The flavanol has remarkable oxidation resistance, can effectively slow down or stop the occurrence of oxidation reaction, and prevents further reaction of free radicals, thereby improving the stability and oxidation resistance of the product. The flavanol can participate in free radical reaction to provide additional hydroxyl groups, and in addition, when the flavanol can be partially decomposed at high temperature, new free radicals can be provided, the cyclization degree of the polymer is increased, the high temperature resistance of the polymer is improved, and the hydroxyl group content, the stability and the high temperature resistance of the modified filler are greatly increased.
(2) According to the scheme, the nonpolar chain is introduced into the system through the modified castor oil, so that the mutual solubility of each component of the polyurethane system is increased, and the adhesive property, heat resistance, water resistance and chemical corrosion resistance of the modified polyurethane adhesive are greatly improved.
(3) The modified castor oil and the modified filler adopted by the scheme of the invention are relatively cheap additives, and the introduction of the modified castor oil and the modified filler can reduce the manufacturing cost of the adhesive.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description is given below with reference to the embodiments, structures, features and effects according to the present invention.
Example 1
The solvent-free environment-friendly modified polyurethane adhesive comprises the following raw materials in parts by weight:
40 parts of polypropylene glycol, 120 parts of liquefied MDI (diphenyl methane diisocyanate), 7 parts of diethanolamine, 1 part of modified castor oil, 1 part of phosphoric acid and 8 parts of modified filler;
the preparation method of the modified filler comprises the following steps:
1) Adding styrene, divinylbenzene, butyl acrylate and hydroxyethyl methacrylate into deionized water, heating to 75 ℃ under nitrogen atmosphere, and stirring and mixing for 30min to obtain a mixed solution;
2) Cooling the mixed solution to 40 ℃, adjusting the pH value to 4.5, adding flavanol and a potassium persulfate aqueous solution with the mass concentration of 99.5% under the nitrogen atmosphere, stirring and reacting for 4 hours, cooling to room temperature, and filtering out gel to obtain emulsion;
wherein the mass ratio of the aqueous solution of styrene, divinylbenzene, butyl acrylate, hydroxyethyl methacrylate, deionized water, flavanol and potassium persulfate is 10:6.7:3.2:8.2:970:1.5:1.2;
3) And (3) centrifuging, drying and grinding the emulsion to obtain the modified filler with the particle size of 400 nm.
The preparation method of the modified castor oil comprises the following steps:
(1) Stirring 2, 3-dimethylbutanol, adipic acid, isophthalic acid, polyether polyol and nano silicon dioxide for 30min at the rotating speed of 250r/min, and reacting for 10h at the temperature of 210 ℃ in a vacuum state to obtain a mixture; wherein the mass ratio of the isophthalic acid to the 2, 3-dimethylbutanediol to the adipic acid to the polyether polyol to the nano silicon dioxide is 10:75:80:8:0.08.
(2) Mixing the mixture and castor oil according to the mass ratio of 2.0:1, and reacting for 3 hours at 210 ℃ under vacuum to obtain the modified castor oil.
The preparation method of the solvent-free environment-friendly modified polyurethane adhesive comprises the following steps: after the modified filler and polypropylene glycol are dispersed for 30min by ultrasonic, heating to 70 ℃ under nitrogen atmosphere, sequentially adding liquefied MDI, diethanolamine, modified castor oil and phosphoric acid, and reacting for 3h to obtain the modified polyurethane adhesive.
Example 2
The solvent-free environment-friendly modified polyurethane adhesive comprises the following raw materials in parts by weight:
47.5 parts of polypropylene glycol, 135 parts of liquefied MDI, 8.5 parts of diethanolamine, 1.5 parts of modified castor oil, 1.5 parts of phosphoric acid and 9 parts of modified filler;
the preparation method of the modified filler comprises the following steps:
1) Adding styrene, divinylbenzene, butyl acrylate and hydroxyethyl methacrylate into deionized water, heating to 78 ℃ under nitrogen atmosphere, and stirring and mixing for 37.5min to obtain a mixed solution;
2) Cooling the mixed solution to 42.5 ℃, adjusting the pH value to 5.0, adding flavanol and a potassium persulfate aqueous solution with the mass concentration of 99.5% under the nitrogen atmosphere, stirring and reacting for 4.5h, cooling to room temperature, and filtering out gel to obtain emulsion;
wherein the mass ratio of the aqueous solution of styrene, divinylbenzene, butyl acrylate, hydroxyethyl methacrylate, deionized water, flavanol and potassium persulfate is 10.5:6.85:3.35:8.5:975:2.0:3.7;
3) And (3) centrifuging, drying and grinding the emulsion to obtain the modified filler with the particle size of 400-500nm.
The preparation method of the modified castor oil comprises the following steps:
(1) Stirring 2, 3-dimethylbutanol, adipic acid, isophthalic acid, polyether polyol and nano silicon dioxide for 38min at a rotating speed of 275r/min, and reacting for 11h at a temperature of 215 ℃ in a vacuum state to obtain a mixture; wherein the mass ratio of the isophthalic acid to the 2, 3-dimethylbutanediol to the adipic acid to the polyether polyol to the nano silicon dioxide is 10.5:78:84:8.5:0.09.
(2) Mixing the mixture and castor oil according to the mass ratio of 2.1:1, and reacting for 3.5 hours at 215 ℃ under vacuum state to obtain the modified castor oil.
The preparation method of the solvent-free environment-friendly modified polyurethane adhesive comprises the following steps: and after the modified filler and the polypropylene glycol are subjected to ultrasonic dispersion for 38min, heating to 72.5 ℃ in a nitrogen atmosphere, sequentially adding liquefied MDI, diethanolamine, modified castor oil and phosphoric acid, and reacting for 4h to obtain the modified polyurethane adhesive.
Example 3
The solvent-free environment-friendly modified polyurethane adhesive comprises the following raw materials in parts by weight:
55 parts of polypropylene glycol, 150 parts of liquefied MDI (diphenyl methane diisocyanate), 10 parts of diethanolamine, 2 parts of modified castor oil, 2 parts of phosphoric acid and 10 parts of modified filler;
the preparation method of the modified filler comprises the following steps:
1) Adding styrene, divinylbenzene, butyl acrylate and hydroxyethyl methacrylate into deionized water, heating to 80 ℃ under nitrogen atmosphere, and stirring and mixing for 45min to obtain a mixed solution;
2) Cooling the mixed solution to 45 ℃, regulating the pH value to 5.5, adding flavanol and a potassium persulfate aqueous solution with the mass concentration of 99.5% under the nitrogen atmosphere, stirring and reacting for 5 hours, cooling to room temperature, and filtering out gel to obtain emulsion;
wherein the mass ratio of the aqueous solution of styrene, divinylbenzene, butyl acrylate, hydroxyethyl methacrylate, deionized water, flavanol and potassium persulfate is 11:7.0:3.5:8.8:980:2.5:5.2;
3) And centrifuging, drying and grinding the emulsion to obtain the modified filler with the particle size of 500nm.
The preparation method of the modified castor oil comprises the following steps:
(1) Stirring 2, 3-dimethylbutanol, adipic acid, isophthalic acid, polyether polyol and nano silicon dioxide for 45min at the rotating speed of 300r/min, and reacting for 12h at 220 ℃ in a vacuum state to obtain a mixture; wherein the mass ratio of the isophthalic acid to the 2, 3-dimethylbutanediol to the adipic acid to the polyether polyol to the nano silicon dioxide is 11:80:88:9:0.1.
(2) Mixing the mixture and castor oil according to the mass ratio of 2.2:1, and reacting for 4 hours at 220 ℃ under vacuum to obtain the modified castor oil.
The preparation method of the solvent-free environment-friendly modified polyurethane adhesive comprises the following steps: and after the modified filler and the polypropylene glycol are subjected to ultrasonic dispersion for 45min, heating to 75 ℃ in a nitrogen atmosphere, sequentially adding liquefied MDI, diethanolamine, modified castor oil and phosphoric acid, and reacting for 5h to obtain the modified polyurethane adhesive.
Comparative example 1
In comparison with example 2, the difference is that comparative example 1 uses castor oil instead of modified castor oil, and the remaining components, preparation steps and parameters are identical.
Comparative example 2
Step (1), stirring and mixing 2, 3-dimethylbutanediol, adipic acid, isophthalic acid, polyether polyol and nano silicon dioxide, and heating for reaction to obtain a mixture;
the difference compared to example 2 is that comparative example 2 does not add castor oil and uses a mixture instead of modified castor oil, the remaining components, preparation steps and parameters are identical.
Comparative example 3
The difference compared to example 2 is that comparative example 3 does not use modified castor oil and the remaining components, preparation steps and parameters are identical.
Comparative example 4
In comparison with example 2, the difference is that comparative example 4 does not employ flavanols, and the remaining components, preparation steps and parameters are identical.
Comparative example 5
The difference compared to example 2 is that the modified filler of comparative example 5 has a particle size of 200nm and the remaining components, preparation steps and parameters are identical.
Comparative example 6
The difference compared to example 2 is that the modified filler of comparative example 6 has a particle size of 100nm and the remaining components, preparation steps and parameters are identical.
Comparative example 7
In comparison with example 2, the difference is that comparative example 7 does not employ modified filler, and the remaining components, preparation steps and parameters are identical.
Comparative example 8
The preparation method of the modified polyurethane adhesive comprises the following steps: and (3) mechanically stirring the modified filler and polypropylene glycol for 2 hours, heating to 72.5 ℃ in a nitrogen atmosphere, sequentially adding liquefied MDI, diethanolamine, modified castor oil and phosphoric acid, and reacting for 4 hours to obtain the modified polyurethane adhesive.
In comparison with example 2, comparative example 7 uses mechanical stirring instead of ultrasonic dispersion, and the remaining components, preparation steps and parameters are identical.
The modified polyurethane adhesives prepared in examples 1 to 3 and comparative examples 1 to 8 were subjected to mechanical property test and viscosity test, respectively, tensile strength test was referred to GB/T528-2008, tensile strong shear strength test was referred to GB/T7124-86, and the test results thereof are shown in Table 1.
TABLE 1
From the test results of Table 1, it is understood that the mechanical properties and viscosity of the modified polyurethane adhesives prepared in examples 1 to 3 are significantly better than those of comparative examples 1 to 8 in examples 1 to 3 as compared with comparative examples 1 to 8.
With reference to table 1, it is known from the analysis of examples 1-3 and comparative examples 1-8 that the introduction of the modified filler with multiple hydroxyl functional groups reduces the viscosity of the modified polyurethane adhesive, and the addition of the modified castor oil increases the mutual solubility of partial components of the system, and at the same time, the modified castor oil has a synergistic effect with the modified filler to improve the rheological property of the adhesive, and the modified castor oil contains more double bonds and triple bonds, can serve as a softener and a plasticizer, and improves the rheological property of the adhesive, thereby improving the fluidity thereof; in addition, the modified filler and the modified castor oil have the synergistic enhancement of the adhesive performance of the adhesive, because the hydroxyl functional groups can react with the modified castor oil to form chemical bonds, thereby enhancing the adhesive performance, tensile strength, shear strength and thermal stability of the adhesive, and in addition, a proper amount of modified castor oil can improve the flexibility and heat resistance of the adhesive.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (10)
1. The solvent-free environment-friendly modified polyurethane adhesive is characterized by comprising the following raw materials in parts by weight:
40-55 parts of polypropylene glycol, 120-150 parts of liquefied MDI (diphenyl methane diisocyanate), 7-10 parts of diethanolamine, 1-2 parts of modified castor oil, 1-2 parts of phosphoric acid and 8-10 parts of modified filler;
the preparation method of the modified filler comprises the following steps:
1) Adding styrene, divinylbenzene, butyl acrylate and hydroxyethyl methacrylate into deionized water, heating and stirring under nitrogen atmosphere to obtain a mixed solution;
2) Pretreating the mixed solution, adding flavanol and potassium persulfate aqueous solution under nitrogen atmosphere, stirring for reaction, cooling to room temperature, and filtering to remove gel to obtain emulsion;
3) And centrifuging, drying and grinding the emulsion to obtain the modified filler.
2. The solvent-free environment-friendly modified polyurethane adhesive according to claim 1, which is characterized in that: in the step 1), the heating condition is heating to 75-80 ℃, and the stirring and mixing time is 30-45min.
3. The solvent-free environment-friendly modified polyurethane adhesive according to claim 1, which is characterized in that: in the step 2), the pretreatment is to cool the mixed solution to 40-45 ℃ and adjust the pH value to 4.5-5.5; the stirring reaction time is 4-5h; the mass concentration of the potassium persulfate aqueous solution is 99.5%.
4. The solvent-free environment-friendly modified polyurethane adhesive according to claim 1, which is characterized in that: in the steps 1) -2), the mass ratio of the styrene, divinylbenzene, butyl acrylate, hydroxyethyl methacrylate, deionized water, flavanol and potassium persulfate aqueous solution is 10-11:6.7-7.0:3.2-3.5:8.2-8.8:970-980:1.5-2.5:1.2-5.2.
5. The solvent-free environment-friendly modified polyurethane adhesive according to claim 1, which is characterized in that: the particle size of the ground modified filler is 400-500nm.
6. The solvent-free environment-friendly modified polyurethane adhesive according to claim 1, wherein the preparation method of the modified castor oil comprises the following steps:
(1) Stirring and mixing 2, 3-dimethylbutanediol, adipic acid, isophthalic acid, polyether polyol and nano silicon dioxide, and heating for reaction to obtain a mixture;
(2) Mixing the mixture with castor oil, and heating to react to obtain the modified castor oil.
7. The solvent-free environment-friendly modified polyurethane adhesive according to claim 6, wherein the solvent-free environment-friendly modified polyurethane adhesive is characterized in that: in the step (1), stirring and mixing conditions are that stirring is carried out for 30-45min at the rotating speed of 250-300 r/min; the heating reaction condition is that the reaction is carried out for 10 to 12 hours under the vacuum state at the temperature of 210 to 220 ℃; the mass ratio of the isophthalic acid to the 2, 3-dimethylbutanediol to the adipic acid to the polyether polyol to the nano silicon dioxide is 10-11:75-80:80-88:8-9:0.08-0.1.
8. The solvent-free environment-friendly modified polyurethane adhesive according to claim 6, wherein the solvent-free environment-friendly modified polyurethane adhesive is characterized in that: in the step (2), the mass ratio of the mixture to the castor oil is 2.0-2.2:1, the heating reaction condition is that the reaction is carried out for 3 to 4 hours under the vacuum state at the temperature of 210 to 220 ℃.
9. A method for preparing the solvent-free environment-friendly modified polyurethane adhesive according to any one of claims 1 to 8, which is characterized by comprising the following steps: and (3) uniformly mixing the modified filler with polypropylene glycol, heating in a nitrogen atmosphere, and sequentially adding liquefied MDI, diethanolamine, modified castor oil and phosphoric acid for reaction to obtain the modified polyurethane adhesive.
10. The method for preparing the solvent-free environment-friendly modified polyurethane adhesive, which is characterized by comprising the following steps of: the uniform mixing condition is ultrasonic dispersion for 30-45min, the heating condition is heating to 70-75 ℃ and the reaction time is 3-5h.
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Denomination of invention: A solvent-free and environmentally friendly modified polyurethane adhesive and its preparation method Granted publication date: 20231208 Pledgee: Agricultural Bank of China Limited Jiangmen Jianghai sub branch Pledgor: GUANGDONG SINO-ADHESIVE NEW MATERIAL TECHNOLOGY Co.,Ltd. Registration number: Y2024980024371 |